M-(3,3-disubstituted ureido) phenyl {8 (substituted)methyl{9 {0 carbamates

ABSTRACT

The present invention relates to novel m-(3,3-disubstituted ureido)phenyl ((substituted)methyl)carbamates. It also relates to a method for controlling undesirable plant species with said compounds and to a process for the preparation thereof.

United States Patent [191 Szabo 1 Dec. 16, 1975 M-(3,3-DISUBSTITUTEDUREIDO) PHENYL [(SUBSTITUTED)METHYL] CARBAMATES [76] Inventor: KarolySzab, Stiegengasse 4/16,,

, A-1060 Vienna, Austria [22] Filed: May 8, 1972 21 Appl. No.: 251,481

[52l US. Cl. 260/479 C; 71/106; 260/453 AL;

3/1969 Wilson et a1 260/479 3,547,979 12/1970 Brantley et al. 260/479Primary Examiner.lames A. Patten Attorney, Agent, or Firm-Harry H. Kline57 ABSTRACT The present invention relates to novel m-(3,3- disubstitutedureido)phenyl [(substituted)methy1]carbamates. It also relates to amethod for controlling undesirable plant species with said compounds andto a process for the preparation thereof.

5 Claims, N0 Drawings 1 2 M-(3,3-DISUBSTITUTED UREIDO) PHENYL sodiumcarbonate, potassium carbonate or triethylaml(SUBSTITUTED)METHYLlCARBAMATES ine. The reaction is slightly exothermic and may notrequireheating; however, it is generally good practice This invention relatesto novel com ounds havin the p g to heat the reaction mixture to refluxtemperature structure: v 5 when the exothenn has subsided. Equimolaramounts 2 of reactants, i.e., isocyanate and ureido phenol, are 0'generally used in the reaction although an excess of either reactant maybe present without seriously affecting the reaction. After refluxing,the solvent is removed from the reaction mixture by evaporation underre- 2 duced pressure. Where desired, the crude product may NH- 9' betriturated with hexane, petroleum ether, or the like, 0 3 andrecrystallized from a solvent, such as toluene, ethanol, benzene, or thelike. The reaction may be illuswhere R represents a member selected fromthe group trated as follows:

2 H- C-N R3 OCN CH2 0 R1 0 II O-CN-CH OR 2 H- g-N R o 3 consisting ofalkyl C -C monohaloalkyl C -C ,'and where R R and R are as previouslydescribed. dihaloalkyl C -C R represents a member selected The ureidophenols utilized in the above reaction are from the group consisting ofalkyl C -C and alkoxy known in the art. Similarly, some of thealkoxymethyl C -C and R is alkyl C -C isocyanates used in thepreparation of the compounds The invention also relates to a method forcontrolling of the present invention are also known. They can beundesirable plant species with the above-identified prepared by reactingthe appropriate halomethylalkyl compounds by (l) applying a herbicidallyeffective ether or halomethyl halosubstituted alkyl ether with amount ofa compound of the above formula to the 40 silver cyanate. The reactionis preferably run in anhyfoliage and plane parts of undesirable plantspecies or drous ether using approximately equimolar amounts of (2)applying a herbicidally effective amount of such the ether and thesilver cyanate. As the reaction is compound to soil containing seedsand/or seedling usually exothermic, it is generally desirable to useexplants of undesirable plant species. temal cooling to maintain thetemperature of the reac- I acwl-dance ith th present i ti th -(3,3- tionmixture below about 20C. and usually between disubstituted ureido)phenyl[(substituted)methyl]carabout 0 and 20C. The reaction may be illustratedas bamates having the formula: follows:

. R.--0 :l-l halo AgOCN RO-CH- O Nco Ag halo where R. is alkyl c.-c,. llmonohaloalkyl C1-C5, or dihaloalkyl C -C 0-C-NH-CH -O-R Thehalomethylalkyl ethers employed in the above reactions can be obtainedby conversion of the appropriate alcohol into its halomethyl derivative,preferably its chloromethyl derivative. This can be accomplished H C byreacting the alcohol with formaldehyde and anhy- R drous hydrogenhalide, preferably HCl gas, at low temo perature, i.e., between about 0and -l0C. Water is where split out of the reaction and can be separatedfrom the 12,, R and R have the following meanings: Organic layer ydecantatwn- R alkyl c c monohaloalkyl c c dihaloalkyl The compounds ofthe present rnvention can beprec c where h i C1 Br, I, or F, butpreferamy pared for appl catlon to vegetation or SOll containing 1 seedsof undesirable plant species. They can be made R2 alkyl c c and alkoxy cc up as dusts or dust concentrates by grinding together R alkyl C -C theactive compound and a diluent, such as attapulgite,

can be prepared by reacting a ureido phenol with an kaolin, bentonite,talc, diatomaceous earth, or the like.

alkoxy or halosubstituted alkoxymethyl isocyanate in Dusts usuallycontain about 1% 15% y Weight of the an anhydrous a r ti l t, h asacetone, h lactive material while the concentrates may containisobutylketone, benzene, toluene, diethyl ether, meth-' from about 25% 05 by eight Of Said material.

ylethylketone in the presence of a weak base, such as These formulationsare particularly useful for control of undesirable plant species whenapplied to soil, containing seeds or seedlings of undesirable plants, inan amount sufficient to provide from about 0.5 to 20 pounds per acre ofthe active material.

Wettable powders are made up in the same manner as dust concentrates,but in addition, they generally also contain about 1% to 5% by weight ofa wetting agent, such as the alkylnaphthalene sulfonates, sulfated fattyalcohols, sulfonated fatty acid esters, and esters of sodiumsulfosuccinate. They also generally contain from about 1% to 5% byweight of a dispersant, such as the lignin sulfonates, polyvinylalcohols, sodium naphthalene sulfonate, or the like. In use theseWettable powder formulations are generally dispersed in water andapplied to vegetation or soil as a liquid spray. For both postemergenceand preemergence applications, it is usually desirable to applysufficient spray to provide about 0.5 to 20 pounds per acre, andpreferably 0.5 to 8 pounds per acre of the active compound.

The compounds of this invention may also be made up in the form ofgranules or pellets. The active compounds can be dissolved in a volatilesolvent, such as acetone, and sprayed on sorptive granules, such asattaclay, ground corn cobs, or heat expanded vermiculite to provideherbicidal granules which can be applied with conventional applicators.

' Herbicidal granules can also be prepared by treating non-sorptivegranules, such as sand or diatomaceous earth, with a binder solution,such as a sugar solution, zinc chloride solution, or the like, andtreating the wetted granules with a dust or dust concentrate containingthe active material. These formulations are, likewise, generally appliedin sufficient amount to provide about 0.5 to 20 pounds per acre ofactive compound.

The following examples are given primarily by way of illustration. Nospecific details or enumerations contained therein should be construedas limitations on the present invention except insofar as they appear inthe appended claims. All parts and percentages are by weight unlessotherwise specifically designated.

EXAMPLE 1 Conversion of Isobutyl Alcohol into its ChloromethylDerivative icmrpu-cmon (01 HCl A mixture of isobutyl alcohol andformaldehyde was cooled to lOC., under nitrogen. Hydrogen chloride wasthen passed with stirring into the reaction mixture for /1 hour and thetemperature of the mixture was maintained at -5 to C. The mixtureseparated into two layers. The lower aqueous layer was separated, andthe organic component dried over anhydrous cal cium chloride. Fractiondistillation using a 12-inch Vigreux column afforded a liquid b.p. 4448C./53 63 mm., yield 413 grams.

EXAMPLE 2 Conversion of 3Pentanol into the Corresponding ChloromethylDerivative A mixture of 50 grams of 3-pentanol and 17 grams ofpara-formaldehyde were placed in a 3-necked roundbottomed flask andcooled by water. Dry hydrogen chloride was passed slowly into themixture while the p-formaldehyde disappeared. The aqueous layer wasseparated and the organic layer dried over anhydrous magnesium sulfateto give grams of crude product. Distillation afforded 67 grams, b.p.5l/l5 20 mm., n 1.4225.

EXAMPLE 3 Preparation of (lsobutoxy)methyl lsocyanate Silver cyanate(170 grams) was suspended in 500 ml. of anhydrous ether and cooled to10C. The reaction vessel was equipped for stirring and provided with acondenser and dropping funnel. To the cold ether and cyanate mixture wasslowly added the chloromethyl isobutyl ether while maintaining thetemperature of the mixture at 10C. The reaction was exothermic and theaddition time was 1 hour. Stirring was continued at room temperature for2 hours and then followed by gentle reflux for another 2 hours. Themixture was cooled and the inorganic salts filtered off and the solventremoved by evaporation. The residue was distilled and gave product withboiling point 39 42C./25 to 30 mm., yield grams.

EXAMPLE 4 Preparation of l-Ethylpropoxy)methyl lsocyanate Silver cyanate(49 grams) was suspended in 200 ml. of anhydrous ether, and gentlystirred using a magnetic stirrer at 10 to 15C. The chloromethylderivative was added dropwise during /2 hour. After the addition wascomplete, the reaction mixture was refluxed for 2 hours. The silver saltwas filtered off and washed with fresh anhydrous ether. The ether wasremoved by evaporation in vacuo on a rotary evaporator.

The residue was distilled, to give a product, b.p. 65 70C. at 25 30 mm.

EXAMPLE 5 Preparation of Methoxymethyl lsocyanate To a suspension ofsilver cyanate (225 grams) in 750 ml. of anhydrous ether. cooled to 1020 and gently stirred using a magnetic stirrer was added dropwisechloromethyl methyl ether (1 10 grams). The reaction was exothermic andaddition time was 1 to 1 /2 hours. After the addition was complete, themixture was stirred for 1 hour at room temperature and refluxed for 2hours.

The inorganic salts were filtered off and the ether carefully distilledoff to give product boiling point 88 91C.. yield, 40 grams.

3,927,070 6 EXAMPLE 6 finally the above isocyanate (0.10 mole) 1.3grams. The mixture warmed slightly and was then refluxed for 1 hour, andthen stirred for another 3 hours. The solvent was removed by evaporationin .vacuo leaving an (CH3)2-((C:SI:L CEXH 2SEICL x 85 oily residue whichwas then triturated with petroleum ether (60 to 70C. bOllll'lg point).The residue hardened to a crystalline mass, and was recrystallized fromchloronlethyl ISPPYOPYI ether was added to ethanol to yield 2.4 grams ofproduct, melting point stlrred suspenslon of silver cyanate (80 grams,excess to 153C 1 51 grams) in anhydrous ether (250 ml.) cooled to C.during /2 hour. After the addition was complete,

the reaction mixture was refluxed for 4 hours. The EXAMPLE 8 inorganicsalts were filtered off and solvent ether removed by evaporation at lowtemperatures around Preparation of (lsopropoxy)methyl IsocyanatePreparation of m-( 3-methoxy-3-methylureido)phenyl V l 5[(1-ethylpropoxy)methyl]carbamate GHQ-CH3 OCH 3 OCN- CH2- O- CH II I 0 3GHQ-CH3 vO H CH2-CH3 I I O-C-N-CHg-O-CH I Caz-CH CH NH-C- The residuewas distilled in vacuo to give a product In a 100 ml. round-bottomedflask were placed 1.96 b.p. 89 91C. Yield, grams, n 1.4010. grams (0.01mole) of the ureido compound. To this 7' 40 was added 25 ml. of acetonefollowed by a few drops of EXAMPLE 7 triethylamine and 1.44 grams of(l-ethylprop0xy)- Preparation of m-( 3-methoxy-3-methylureido)phenylmethyl isocyanate (0.10 mole). The reaction mixture(isobutoxymethyl)carbamate warmed slightly and was then heated underreflux for l OCHB OCN-CH -O-CH -CH-CH O H CH8 II I i O- C-N- CH2- 0- CH-CH-CH M. NH-C-NK H j lna ml. flask were placed 1.96 grams (0.10 mole)hour. The solvent was removed by evaporation in of 3-(m-hydroxyphenyl)-lmethoxy-l-methylurea. To vacuo and the residue therefrom triturated withhexthis was added 15 ml. of acetone (anhydrous), followed ane. When awhite solid product was obtained, it was by two to three drops ofanhydrous triethylamine, and filtered off and recrystallized fromtoluene to yield 3.3

grams (68%) of product melting at 1 1 1 to l 14C.

EXAMPLE 9 Preparation of m-( 3-methoxy-3-methylureido)phenyl In a 100ml. round-bottomed flask were placed 1.96 grams of the above ureidocompound (0.01 mole) dissolved in 10-15 ml. of acetone. Themethoxymethyl isocyanate (0.88 grams, 0.01 mole) was then added to themixture, followed by the addition of three drops of triethylamine. Thereaction is slightly exothermic. After the reaction had subsided themixture was refluxed for an hour with stirring. Stirring was continuedfor another 3 hours after reflux and then the solvent was removed byevaporation under vacuo. The residue was triturated with hexane. When awhite crystalline product resulted, it was recrystallized from tolueneto yield a product melting at 109 to 112C., yield 2.4 grams (85%).

8 EXAMPLE 10 Preparation of m-( 3-methoxy-3-methylureido)phenyl(isopropoxymethyl )carbamate In a 100 ml. round-bottomed flask wereplaced 1.96 grams of the ureidophenol (0.01 mole) and 25 ml. of acetone.To the acetone solution were added a few drops of triethylamine,followed by addition of the above isocyanate (isopropoxymethylisocyanate), 1.16 grams (0.10 mole). The mixture warmed slightly and wasrefluxed for 1 hour. The solvent was removed by evaporation in vacuo ona rotary evaporator and the residue was triturated with hexane to yielda crystalline material. The product was filtered off and recrystallizedfrom benzene to yield 2 grams (64%) of product melting at 129 to 131C.

Following the above procedure and substituting the appropriate ureidophenols and alkoxymethyl isocyanates in the reaction yields the productsset forth in Table 1 below.

TABLE 1 TABLE I-continued The postemergence herbicidal activity of thecompounds of the present invention is demonstrated by the followingtests. In said tests, ten-day old crabgrass, yellow foxtail, wild oats,mustard, bindweed and bush bean plants are sprayed with 35%/65%water/acetone solutions of test compound. Each flat was sprayed withTABLE II Postemergence Activity Kill Indian Compound CrabgrassWatergrass Mustard Corn Wild Oats Curled Dock Bush Bean 0 H II IO-C-N-CH -OCH lOO LB 100 DF MI OCH TABLE II -continued PostemergenceActivity Kill Indian Compound Crabgrass Watergrass Mustard Corn WildOats Curled Dock Bush Bean H CH u 3 Q-C-N-CHQ-O-EH LB o 1.3 100 Ml /0CH3NH- c- N DF Dead Foliage LB Leaf Burn Ml Moderate Injury EXAMPLE l2Plant Species:

The postemergenceherbicidal activity of the com- COR com pounds of thepresent invention IS demonstrated by the W0 wild following tests. Avariety of monocotyledonous and gQ dicotyledonous plants, approximately2 weeks old and Ml foxtail millet growing in flats, are sprayed with35%/65% aqueous ag acetone mixtures containing the surfactant Tween 20LA iambsquaners added to 0.5% v/v, and test compound in sufficientconcentration to provide the equivalent of 0.5 1.0 or

7: Difference 4.0 pounds of active compound per acre, when sprayed inGrowth on-the flats for a given period under 86 ps1 pressure. RatingSystem: from the Check After spraying, the flats are placed ongreenhouse 0 no effect 0 benches and cared for in accordance with normal1 i l effect 1-10 greenhouse practices. Three weeks after treatment, the3 effect d d h d 3 moderate effect 26-40 plants are examined an rateaccor mg to t e in ex 5 d fi i injury 414,0 given below. The data arereported in Table III. 6 herbicidal effect 61-75 7 good herbicidaleffect 76-90 8 approaching complete kill 9l-99 9 Complete kill lOO PlantSpecies: 4 abnormal growth. i.e., a definite physiological malformationbut with an overall effect less than a 5 on the MG annual morning-gloryrating scale. COT cotton SB sugar beet Based on visual determination ofstand. sizev vigor. chlorosis. growth malforma- SOY soybean tion. andover-all plant appearance,

TABLE III Postemergence l-Ierbicidal Activity Ratings lbs/acre CompoundRate MG COT SB SOY COR WO BA FOX MI RAG MU LA ii I O-C-N-CH -OCH O5 9 99 7 9 7 3 l 8 9 9 8 l O 9 9 9 9 5 8 8 8 8 9 9 9 4 0 9 9 9 9 9 9 9 8 9 99 9 OCH NH- C N o H c 2 H 5 II I u -C-NCH -O-CH O5 9 9 9 9 9 9 9 9 9 9 99 H l O 9 9 9 9 7 9 9 9 9 9 9 9 2 5 4 0 9 9 9 9 7 9 9 9 9 9 9 9 OCH 3NH- C- N TABLE III-continued Postemergence Herbicidal Activity Ratingslbs/acre Compound Rate MG COT SB SOY COR wo BA FOX Ml RAG MU LA 8 *1O-C-N-CH2-O-CH2-CH 0.5 9 9 3 o 0 6 s 3 9 9 0 1.0 9 9 1 9 2 9 s 8 7 9 9 24.0 9 9 s 9 9 9 9 9 9 9 9 8 NH c N/CH3 ll \CH3 0 H c1-1 I l 1 3 O-C-N-CH-O-CH-CH-CH -Cl 0.5 9 9 9 9 5 1 1 s 6 9 9 s E. 1.0 9 9 9 9 6 8 1 s 6 9 9s 4.0 1 3 7 9 9 9 s 9 s 9 9 8 NH c N/CH3 of test com ound. Thistreatment rovides the e uiva- EXAMPLE 13 P P q lent of pounds per acreof test compound. After The preemergence herbicidal activity of thecomspraying, the flats are placed on greenhouse benches nd pounds of thepresent invention is demonstrated by the cared for in accordance withconventional greenhouse following tests. In said tests, seeds ofcrabgrass, corn, procedures. Three weeks after spraying, the flats arewatergrass, wild oats, bush beans, Indian mustard, and examined andrated for herbicidal activity. The data curled dock are planted inflats. The seeded flats are are reported in Table IV below. then sprayedwith an acetone/water mixture and mg. 35

TABLE IV Preemergence Activity 7: Kill Crab- Waterlndian Wild CurledBush Compound grass grass Mustard Oats Corn Dock Bean 0 H II O-C-N-CH-O- CH OCH NH- fi-N 0 H C H l l l 2 5 -C-N-C H -O-CH 2 5 I00 I00 100 I00100 I00 100 NH C N OCH3 O H I l O-C-N-CH -O-CH -CH CH lOO 100 100 I00100 100 ST [0 CH 0C H Ml 3 NH- C N u c H O 3 ST Stunting lG InhibitsGermination CH Chlorosis Ml Moderate Injury EXAMPLE 14 The preemergenceherbicidal activity of the compounds of the invention is demonstrated inthe following tests. Seeds of a variety of monocotyledonous anddicotyledonous plants are mixed with potting soil and planted in plasticpots in the top one inch of potting soil. The seeded pots are thensprayed with a test solu- TABLEV Preemergence Herbicidal ActivityRatings lbs/acre Compound Rate MG 813 SOY COR wo BA FOX Ml RAG MU LA 0 HII I o- -N- m c CH2 0 3 0.5 8 5 5 7 o 7 8 7 5 5 9 7 1.0 9 8 8 9 2 8 9 96 9 9 8 4.0 9 9 9 9 9 9 9 9 9 9 9 9 0m 3 NH-E-N 0 H c H I I l 5 0.5 3' 3o 0 0 3 8 7 0 8 9 8 E H 1.0 5 7 9 5 5 7 8 9 1 9 9 8 2 5 4.0 9 9 9 9 9 99 9 9 9 9 9 /0CH3 NH-C-N 0 H I I 0.5 1 0 o 2 0 2 7 9 1 9 9 7 1.0 9 0 6 51 9 9 9 9 9 9 9 4.0 9 9 9 9 9 9 9 9 9 9 9 9 001 NH-fi-N o H CH 11 1 3Q-C-N-CHZ-O-CH I cH 0.5 3 0 6 7 8 8 5 9 9 9 1.0 9 8 9 7 7 7 8 9 8 9 9 8ICC: 4.0 9 9 9 9 9 9 9 9 9 9 9 9 NH-C-N\ 0 H CH3 II I l0-C-N-CH2-O-CHCH2-CH2-CH3 0.5 1 2 0 1 2 0 1 1 0 9 9 8 1.0 3 1 9 8 0 6 79 6 9 9 9 4.0 9 9 9 8 3 8 9 9 7 9 9 9 NH c N/OCH3 0 H cH c1 u 1 1 2 0.50 0 0 0 0 2 3 2 1 3 9 5 a 1 1.0 6 9 8 7 8 5 6 9 3 9 9 8 4.0 9 9 9 9 9 99 9 8 9 9 9 3 NH-C-N o H I 2' 2' 2' 0.5 0 0 1 2 0 5 1 6 3 1 3 1 1.0 9 38 9 0 7 6 9 5 8 9 6 4.0 9 9 9 9 9 9 9 9 9 9 9 9 3 NH-C-N I o OCH3

1. A COMPOUND: M-(3-METHOXY-3-METHYL UREIDO)PHENYL(METHOXY)METHYL)CARBAMATE.
 2. A compound: m-(3-methoxy-3-methylureido)phenyl ((1-ethylpropoxy)methyl)carbamate.
 3. A compound:m-(3-methoxy-3-methyl ureido)phenyl (isobutoxymethyl)carbamate.
 4. Acompound: m-(3-methoxy-3-methyl ureido)phenyl(isopropoxymethyl)carbamate.
 5. A compound: m-(3,3-dimethylureido)phenyl ((2-chloro-1-methylethoxy)methyl)carbamate.